CN114685762B - Preparation method of hydrophobic bisphosphite organic polymer - Google Patents
Preparation method of hydrophobic bisphosphite organic polymer Download PDFInfo
- Publication number
- CN114685762B CN114685762B CN202210446279.0A CN202210446279A CN114685762B CN 114685762 B CN114685762 B CN 114685762B CN 202210446279 A CN202210446279 A CN 202210446279A CN 114685762 B CN114685762 B CN 114685762B
- Authority
- CN
- China
- Prior art keywords
- bisphosphite
- solvent
- hydrophobic
- reaction
- organic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1422—Side-chains containing oxygen containing OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/412—Yamamoto reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The invention discloses a preparation method of a hydrophobic bisphosphite organic polymer, which comprises the following steps: (1) halogenation reaction: obtaining a halogenated monophosphite ligand precursor; (2) esterification reaction: mixing and dissolving halogenated monophosphite ligand precursor, acid binding agent and solvent B in inert gas atmosphere, adding PCl 3 Or PBr 3 Reacting, extracting by an organic solvent, washing an organic layer by saturated saline water, concentrating in vacuum, drying and purifying to obtain a monophosphite ligand; (3) Polymer Synthesis: dissolving a monophosphite ligand in a pore-forming solvent under inert gas atmosphere, adding a coupling catalyst into the mixture to react, filtering, drying, washing solid, performing Soxhlet extraction, and then performing vacuum drying to obtain a hydrophobic bisphosphite organic polymer; the preparation method is simple and convenient, the raw materials are easy to obtain as long as three steps of reactions are performed, the format reagent and noble metal catalysis are not used, and the preparation method is safe and reliable and has low cost.
Description
Technical Field
The invention belongs to the technical field of phosphorus-containing organic polymers, and particularly relates to a preparation method of a hydrophobic bisphosphite organic polymer.
Background
Bidentate phosphorus-containing ligands have important and wide-ranging applications in metal complex catalysis, for example: the bidentate phosphorus-containing ligand and rhodium coordinate to catalyze olefin hydroformylation reaction, and the bidentate phosphorus-containing ligand and Pd coordinate to catalyze Suzuki-Miyaura coupling reaction. Catalytic systems based on bidentate phosphorus-containing ligands have higher chemo-and stereoselectivity than monodentate phosphorus-containing ligands. However, the metal-phosphorus ligand complex is conventionally applied in a homogeneous system, so that the complex is difficult to recycle, the mutual synergistic effect of the ligands can be influenced by a common immobilization method, the surface concentration is low, and the complex is easy to run off.
The problem of recycling can be solved by polymerizing bidentate phosphorus-containing ligands of specific structure to form insoluble polymers which should also possess porosity and high specific surface area for applications in the field of heterogeneous catalytic reactions.
In 2012, tan Bien (macromolecules, 2011,44 (8), 2410) successfully synthesized phosphorus-containing braided aromatic polymers KAPs having a porous structure using benzene and triphenylphosphine, with phosphine ligands uniformly distributed in the polymer bulk phase. But because of the large amount of Lewis acid FeCl used in the preparation process 3 As a polymerization catalyst, the post-cleaning consumes a large amount of solvent and is not easy to remove FeCl 3 Residual FeCl 3 The performance of the supported catalyst of KAPs polymers can be severely affected.
The patents CN103288995A and CN103965386a provide a new method for preparing phosphorus-containing ligand polymer materials, in which vinyl functionalized monophosphine or biphosphine ligands are dissolved in a pore-forming solvent, and a polymerization initiator is added to carry out solvothermal polymerization. The content of phosphine in the polymer body obtained by this method is very high since no other monomer than phosphine ligand is used. However, the vinyl skeleton material is prepared by Grignard reagent, and the preparation process is safe and high in cost, and is not beneficial to mass preparation and production.
In 2016, shore harvest (chem., 2016 (1), 628) a vinyl-functionalized hydrophobic phosphite monomer was synthesized and the corresponding homopolymer was obtained. The reason for the hydrophobicity is that tertiary butyl groups are introduced, so that the problem that phosphite ligands are easy to decompose when meeting water is solved. However, the whole preparation process is complicated and is not beneficial to the amplified preparation.
In the traditional vinyl polymerization method, a double bond functional group solvothermal reaction polymerization reaction is utilized, the original bisphosphite structure of the ligand is kept unchanged in the polymerization process, and a second monomer such as vinyl benzene or vinylated triphenylphosphine is used in the reaction process, wherein the reaction principle is as follows:
disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrophobic bisphosphite organic polymer, which has the advantages of easily available raw materials, no use of Grignard reagent and noble metal catalysis, safety and reliability and low cost.
A method for preparing a hydrophobic bisphosphite organic polymer, comprising the steps of:
(1) Halogenation reaction: adding a solvent A into the monophosphite ligand precursor at the temperature of between 20 ℃ below zero and 80 ℃, adding a halogenated reagent into the monophosphite ligand precursor after dissolution, carrying out heat preservation and stirring reaction for 0.5 to 72 hours, carrying out vacuum concentration, adding the solvent A for redissolving, and purifying to obtain the halogenated monophosphite ligand precursor;
(2) Esterification reaction: mixing and dissolving halogenated monophosphite ligand precursor, acid binding agent and solvent B in inert gas atmosphere at-80-160 deg.c, adding PCl 3 Or PBr 3 Stirring at constant temperature for 0.5-72 hr, adding water or acidic solution to stop the reaction, extracting with organic solvent, washing the organic layer with saturated saline solution, vacuum concentrating, and concentrating with anhydrous Na 2 SO 4 、CaCl 2 Or MgSO 4 Drying and purifying to obtain a monophosphite ligand;
(3) And (3) polymer synthesis: dissolving monophosphite ligand in pore-forming solvent in inert gas atmosphere, adding coupling catalyst, stirring at-20-170 deg.c for 0.1-200 hr, adding water or acid solution to stop the reaction, filtering and using anhydrous Na 2 SO 4 、CaCl 2 Or MgSO 4 Drying, and adding water or absolute ethanol or absoluteWashing the solid with methanol, extracting with Soxhlet for 12-72h, and vacuum drying to obtain hydrophobic bisphosphite organic polymer; the monophosphite ligand precursor comprises any one of compounds 1-6 shown in the following structural formula:
wherein R is 1 ＝H，Me，Et，Pr；R 2 ，R 3 ＝H，iPr，tBu；X 2 ＝N，O，S。
Preferably, the monophosphite ligand precursor in the step (1) adopts compounds 1-6, and the monophosphite ligand obtained in the step (2) corresponds to compounds L-1 to L-6 shown in the following structural formulas:
wherein X is 1 ＝F，Cl，Br，I；
The hydrophobic bisphosphite organic polymers obtained in the step (3) correspond to the compounds POL-1 to POL-6 shown in the following structural formulas respectively:
preferably, the molar ratio of the halogenating agent to the monophosphite ligand precursor is from 0.1 to 10.
Preferably, in step (2), PCl 3 The mol ratio of the halogenated monophosphite ligand precursor to the acid binding agent is 1 (2-6): 4-12.
Preferably, the acid binding agent is triethylamine, pyridine, benzothiazole, naOH, KOH or potassium carbonate.
Preferably, the solvent B is any one or more of methanol, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, N-hexane, petroleum ether, ethyl acetate, N-dimethylformamide, acetone, benzene or benzene homologs and 1, 2-dichloroethane.
Preferably, in step (3), the monophosphite ligand: pore-forming solvent: the mass ratio of the coupling catalyst is 1: (1.5-100): (0.01-10).
Preferably, the coupling catalyst is tris (triphenylphosphine) nickel (formula C 54 H 45 NiP 3 ) Bis- (1, 5-cyclooctadiene) nickel (formula: ni (cod) 2 Or Ni (C) 8 H 12 ) 2 ) Bis (triphenylphosphine) - (1, 5-cyclooctadiene) nickel (formula: ni (cod) (PPh 3 ) 2 Or Ni (C) 8 H 12 )(C 18 H 15 P) 2 ) Bis (1, 2-bis (4-trifluoromethylstyrene) ethylene) nickel (formula: ni (C) 16 H 10 F 6 ) 2 ) Or bis (triphenylphosphine) ethylene nickel (formula: ni (C) 2 H 4 )(PPh 3 ) 2 ) One of them.
Preferably, the pore-forming solvent is at least one of methanol, ethanol, acetonitrile, tetrahydrofuran, ethyl acetate, N-dimethylformamide, acetone, N-methylpyrrolidone, benzene or a benzene homolog, biphenyl, bipyridine, and 1, 2-dichloroethane.
Preferably, the halogenated reagent of step (1) is F 2 、Cl 2 、Br 2 、I 2 HCl, HBr, N-iodosuccinimide, N-bromosuccinimide, N-chlorosuccinimide, methyl iodide or methyl bromide; the solvent A is acetonitrile or tetrahydrofuran.
Preferably, the purification adopts silica gel column chromatography purification or solvent recrystallization method; the silica gel in the silica gel column chromatography purification is 100-400 meshes of silica gel; the chromatographic agent used in the silica gel column chromatography purification or the recrystallization solvent used in the solvent recrystallization method is one or more of absolute methanol, absolute ethanol, ethyl acetate, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, normal hexane, petroleum ether and N, N-dimethylformamide.
Preferably, the acidic solution in step (3) is a dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, acetic acid or ammonium chloride solution, as long as the pH is acidic.
Preferably, the vacuum drying in step (3) is carried out at 20-80 ℃ for 2-48h.
The preparation method provided by the invention takes the monophosphite ligand as a polymerization unit, and the polymer with a bisphosphite ligand structure is obtained through polymerization, which is fundamentally different from a method of directly using bisphosphite ligand for polymerization, the polymerization principle of the method is Yamamoto coupling reaction of halogenated hydrocarbon, the adopted monophosphite ligand forms a brand new bisphosphite structure in the polymerization process, and only one polymerization unit is used in the polymerization process, and the reaction mechanism is shown in the following scheme 1:
the invention has the advantages that:
(1) The preparation method is simple and convenient, the raw materials are easy to obtain as long as three steps of reactions are performed, the format reagent and noble metal catalysis are not used, the preparation method is safe and reliable and has low cost, and the vinyl polymerization method in the prior art needs seven steps of reactions for preparing the phosphorus-containing organic polymer material;
(2) The preparation method provided by the invention takes the monophosphite ligand as a polymerization unit, and the polymer with the bisphosphite ligand repeat unit structure is obtained through C-C coupling polymerization, which is fundamentally different from the method of directly using bisphosphite ligand for polymerization, and the theoretical content of the bisphosphite structure in the final unit volume of polymer is higher and the distribution is more uniform.
Drawings
FIG. 1 crude 2-bromo-4, 6-di-tert-butylphenol (1 a-Br) 1 H NMR spectrum.
FIG. 2 GC-MS spectrum of 2-bromo-4, 6-di-tert-butylphenol (1 a-Br) in the crude product.
FIG. 3 tris (2-bromo-4, 6-di-t-butylphenyl) phosphite (L-1 a-Br) 1 H NMR spectrum.
FIG. 4 tris (2-bromo-4, 6-di-t-butylphenyl) phosphite (L-1 a-Br) 13 C NMR spectrum.
FIG. 5 tris (2-bromo-4, 6-di-t-butylphenyl) phosphite (L-1 a-Br) 31 P NMR spectrum.
FIG. 6 tris (3, 5,3',5' -tetra-tert-butyl-2, 2' -biphenol) phosphite polymer (L-1 a-Br) 13 C MAS NMR spectra.
Detailed Description
Example 1
The monophosphite ligand precursor uses 2, 4-di-tert-butylphenol (denoted as compound 1 a) as R in the compound 1 according to the invention 2 、R 3 Is tBu, R 1 A compound which is H. Preparing a tris (3, 5,3',5' -tetra-tert-butyl 2,2' -biphenol) phosphite polymer (POL-1 a) from 2, 4-di-tert-butylphenol (1 a);
a preparation method of a hydrophobic bisphosphite organic polymer POL-1a comprises the following steps:
(1) Halogenation reaction: 100mL of acetonitrile was added to 10.3g (0.05 mol) of 2, 4-di-tert-butylphenol (1 a) at 25℃and, after dissolution, 8.9g (0.05 mol) of N-bromosuccinimide was slowly added thereto as a halogenating agent, and the reaction was carried out with stirring at a constant temperature for 72 hours, and concentrated in vacuo to give a crude product, see Scheme 3:
the crude product of step (1) is magnetized with liquid nuclei 1 Characterization by both H NMR and chromatography-mass spectrometry GC-MS (see FIGS. 1 and 2), FIG. 1 shows, 1 H NMR(400MHz,CDCl 3 ) 7.29 (dd, j=2.4, 1.0hz,1 h), 7.20 (dd, j=2.5, 1.0hz,1 h), 1.37 (d, j=1.1 hz,9 h), 1.25 (d, j=1.0 hz,9 h); as can be seen from FIG. 2, the m/z value of 2-bromo-4, 6-di-t-butylphenol (1 a-Br) (NIST mass spectrum database): 269,271,57, detected m/z value: 269.1,57.1. As can be seen from FIGS. 1 and 2, the product corresponds to the target product 2-bromo-4, 6-di-tert-butylphenol (1 a-Br), and the bromo product contains a small amount of N-bromosuccinimide; acetonitrile is added into the crude product to be dissolved again, and the 2-bromo-4, 6-di-tert-butylphenol (1 a-Br) is obtained after silica gel column chromatography purification
(2) Esterification reaction: in an argon atmosphereAfter 14.3g (0.05 mol) of 2-bromo-4, 6-di-tert-butylphenol (1 a-Br), 20.77g (0.15 mol) of potassium carbonate (acid-binding agent) were dissolved in methylene chloride at 40℃and 2.33g (0.017 mol) of PCl were slowly added thereto 3 Stirring at constant temperature for 72 hr, adding 50mL ammonium chloride aqueous solution to stop the reaction, extracting with ethyl acetate for 3 times, each time with 100mL ethyl acetate, washing the organic layer with saturated saline solution, vacuum concentrating, and concentrating with anhydrous Na 2 SO 4 Drying and purifying by silica gel column chromatography to obtain the monophosphite ligand: tris (2-bromo-4, 6-di-tert-butylphenyl) phosphite (L-1 a-Br), the liquid nuclear magnetic patterns of the corresponding products are shown in FIGS. 3-5, and the reaction process is shown in Scheme 4:
as can be seen from the figure 3 of the drawings, 1 H NMR(400MHz,CDCl 3 ) Delta 7.40 (d, j=2.5 hz, 3H), 7.28 (dd, j=8.4, 2.0hz, 3H), 1.41 (s, 27H), 1.33 (s, 27H); as can be seen in figure 4 of the drawings, 13 C NMR(101MHz,CDCl 3 )δ151.58(d,J C-P ＝4.0Hz),143.6,131.2,125.17,123.12,116.85(d,J C-P =18.3 Hz), 36.97,36.14,33.23,31.91; as can be seen from figure 5 of the drawings, 31 p NMR (162 MHz): 129.23 (s, 1P) ppm. It is known that the product in the step (2) corresponds to the target product;
(3) And (3) polymer synthesis: 6.47g (0.01 mol) of tris (2-bromo-4, 6-di-t-butylphenyl) phosphite (L-1 a-Br) was dissolved in 64.7g (72 mL) of toluene as a porogen under an argon atmosphere, and 0.65g of Ni (cod) was added thereto 2 The method comprises the steps of carrying out a first treatment on the surface of the Stirring at 60deg.C for 72 hr, adding 0.01mol/L diluted hydrochloric acid 10mL to stop reaction, filtering, and adding anhydrous Na 2 SO 4 Drying, washing the solid by using absolute ethyl alcohol, performing Soxhlet extraction for 72 hours by using diethyl ether as a solvent, and then performing vacuum drying at 60 ℃ for 20 hours to obtain the hydrophobic bisphosphite organic polymer: tris (3, 5,3',5' -tetra-tert-butyl 2,2' -biphenol) phosphite polymer (POL-1 a), corresponding 13 The C MAS NMR spectrum is shown in FIG. 6, and the reaction process is shown in Scheme 5:
as can be seen from fig. 6, the product of step (3) corresponds to the target product;
in the embodiment, the silica gel column chromatography is used for purification, the adopted silica gel is sieved by a 200-400-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and ethyl acetate according to the mass ratio of 20:1.
Example 2
The monophosphite ligand precursor employs 2-tert-butylphenol, designated compound 1c, R in the present invention, compound 1 2 Is tBu, R 1 、R 3 Preparing a tris (3, 3 '-di-tert-butyl-2, 2' -biphenol) phosphite polymer (POL-1 c) from 2-tert-butylphenol as a compound H;
a preparation method of a hydrophobic bisphosphite organic polymer POL-1c comprises the following steps:
(1) Halogenation reaction: 100mL of acetonitrile is added into 0.5mol of 2-tertiary butyl phenol (1 c) at 80 ℃, after the acetonitrile is dissolved, 0.2mol of N-bromosuccinimide is slowly added into the mixture as a halogenating reagent, the mixture is stirred for reaction for 0.5h under heat preservation, the mixture is concentrated in vacuum, acetonitrile is added into the mixture to be dissolved again, and the mixture is recrystallized and purified for 3 times by using absolute ethyl alcohol at 60 ℃ and 50mL of the mixture is used for each time, thus obtaining 2-bromo-6-tertiary butyl phenol (1 c-Br);
(2) Esterification reaction: after 0.06mol of 2-bromo-6-tert-butylphenol (1 c-Br) obtained in step (1) and 0.12mol of potassium carbonate (acid-binding agent) were dissolved in methylene chloride under an argon atmosphere at 160℃and 0.03mol of PCl was slowly added thereto 3 The reaction was stirred at constant temperature for 72h, quenched by the addition of 50mL of aqueous ammonium chloride, extracted 3 times with 100mL of ethyl acetate each time, and then the organic layer was washed with saturated brine, dried over anhydrous MgSO 4 Drying, vacuum concentration and isopropanol recrystallization purification (3 times with 50mL of isopropanol at 70 ℃ each time) to obtain tris (2-bromo-6-tert-butylphenyl) phosphite (L-1 c-Br):
(3) And (3) polymer synthesis: 5g of tris (2-bromo-6-t-butylphenyl) phosphite (L-1 c-Br) was dissolved in 500g of N, N-dimethylformamide as a porogenic solvent, and 50g of Ni (cod) catalyst was added thereto 2 Stirring at 20 ℃ for reaction for 72 hours, adding 100mL of water to stop the reaction, filtering, washing the obtained solid with 100mL of absolute ethyl alcohol, extracting with acetone for 72 hours, and drying in vacuum at 80 ℃ for 2 hours to obtain the hydrophobic bisphosphite organic polymer: tris (3, 3 '-di-tert-butyl-2, 2' -biphenol) phosphite polymer (POL-1 c):
example 3
The monophosphite ligand precursor was 2, 4-di-tert-butylphenol (designated compound 1 a) as in example 1.
A preparation method of a hydrophobic bisphosphite organic polymer POL-1a comprises the following steps:
(1) Halogenation reaction: adding 100mL of acetonitrile into 1.0mol of 2, 4-di-tert-butylphenol (1 a) at 25 ℃, dissolving, slowly adding 0.1mol of N-chlorosuccinimide serving as a halogenated reagent into the mixture, carrying out heat preservation and stirring for reaction for 72h, and carrying out vacuum concentration and silica gel column chromatography purification to obtain 2-chloro-4, 6-di-tert-butylphenol (1 a-Cl);
(2) Esterification reaction: after 60mmol of 2-chloro-4, 6-di-tert-butylphenol (1 a-Cl) obtained in step (1) and 9.5g (120 mmol) of pyridine (acid-binding agent) were dissolved in methylene chloride under an argon atmosphere at 30℃10mmol of PCl was slowly added thereto 3 The reaction was stirred at constant temperature for 72h, quenched by the addition of 50mL of aqueous ammonium chloride, extracted 3 times with 100mL of ethyl acetate each time, and the organic layer was washed with saturated brineAnhydrous CaCl 2 Drying, vacuum concentrating, and purifying by silica gel column chromatography to obtain chloro substituted monophosphite ligand: tris (2-chloro-4, 6-di-tert-butylphenyl) phosphite (L-1 a-Cl);
(3) And (3) polymer synthesis: under an argon atmosphere, 5g of tris (2-chloro-4, 6-di-t-butylphenyl) phosphite (L-1 a-Cl) was dissolved in 1.5g of dimethyl sulfoxide as a porogenic solvent, and 0.05g of Ni (cod) as a catalyst was added thereto 2 Stirring at-20deg.C for 72 hr, adding 10mL of ammonium chloride aqueous solution to stop reaction, filtering, and adding anhydrous CaCl 2 Drying, washing the solid with 20mL of absolute ethanol, soxhlet extraction with diethyl ether for 72 hours, and vacuum drying at 80℃for 2 hours gave the same hydrophobic bisphosphite organic polymer as in example 1: tris (3, 5,3',5' -tetra-tert-butyl-2, 2' -biphenol) phosphite polymer (POL-1 a);
in the embodiment, the silica gel column is used for chromatographic purification, the adopted silica gel is sieved by a 200-400-mesh sieve, and the chromatographic agent is mixed liquid of petroleum ether and ethyl acetate according to the mass ratio of 20:1.
Example 4
The monophosphite ligand precursor uses 2, 4-di-tert-butylphenol (compound 1 a) to prepare tri (3, 5,3',5' -tetra-tert-butylbiphenyl) phosphite polymer (POL-1 a) from 2, 4-di-tert-butylphenol (1 a);
a process for preparing a hydrophobic bisphosphite organic polymer POL-1a, which is substantially the same as in example 1, differs from example 1 in the catalyst and solvent:
in the step (1), tetrahydrofuran is used for replacing acetonitrile; in the step (2), triethylamine is adopted to replace potassium carbonate and PBr is adopted 3 Instead of PCl 3 Tetrahydrofuran is adopted to replace dichloromethane; in the step (3), bis (1, 2-bis (4-trifluoromethylstyrene) ethylene) nickel (chemical formula: ni (C) 16 H 10 F 6 ) 2 ) Instead of bis- (1, 5-cyclooctadiene) nickel (formula: ni (cod) 2 ) DMF is used for replacing toluene, and the reaction is carried out in the step (3)Tetrahydrofuran was used instead of toluene as the pore solvent, and the remainder was the same as in example 1.
Example 5
The monophosphite ligand precursor uses 2, 4-di-tert-butylphenol (1 a) to prepare tris (3, 5,3',5' -tetra-tert-butylbiphenyl) phosphite polymer (POL-1 a) from 2, 4-di-tert-butylphenol (1 a).
A process for preparing a hydrophobic bisphosphite organic polymer POL-1a, which is substantially the same as in example 1, differs from example 1 in the purification method: the halogenated product of step (1) and the esterified product of step (2) were purified, and recrystallized (absolute ethyl alcohol, isopropyl alcohol as solvent) was used instead of silica gel column chromatography, and the other steps were the same as in example 1, and the specific steps are as follows:
(1) Purification in step (1): recrystallizing with absolute ethanol for 3 times, and using 20mL absolute ethanol at 60deg.C each time;
(2) Purification in step (1): the purification was performed 3 times by recrystallization from isopropanol, each time with 20mL of isopropanol at 60 ℃.
Example 6
The monophosphite ligand precursor adopts 3-hydroxy-4-tertiary butyl pyridine (shown as a compound 2 a) as R in the compound 2 2 Is tBu, R 1 A compound which is H;
a preparation method of a hydrophobic bisphosphite organic polymer POL-2a comprises the following steps:
(1) Halogenation reaction: 100mL of acetonitrile is added into 0.1mol of 3-hydroxy-4-tert-butylpyridine (2 a) at 80 ℃, 17.8g (0.1 mol) of N-bromosuccinimide is slowly added into the mixture as a halogenating reagent after the mixture is dissolved, the mixture is stirred and reacted for 36 hours under heat preservation, the mixture is concentrated in vacuo, acetonitrile is added into the mixture to be dissolved again, and the mixture is purified by silica gel column chromatography to obtain 2-bromo-3-hydroxy-4-tert-butylpyridine (2 a-Br);
(2) Esterification reaction: dissolving 0.06mol of 2-bromo-3-hydroxy-4-tert-butylpyridine (2 a-Br) obtained in the step (1) and triethylamine (acid binding agent) in ethanol under argon atmosphere at minus 80 ℃, and slowly adding PCl into the mixture 3 Wherein PCl 3 The mol ratio of the 2-bromo-3-hydroxy-4-tert-butylpyridine to the acid binding agent is 1:2:4, the reaction is carried out for 72h under heat preservation and stirring, 100mL of water is added to stop the reaction, and the reaction is carried out by extracting with ethyl acetate, washing the organic layer with saturated saline solution and anhydrous CaCl 2 Drying, vacuum concentrating, and purifying by silica gel column chromatography to obtain tri (2-bromo-3-hydroxy-4-tert-butylpyridine) phosphite (L-2 a-Br);
(3) And (3) polymer synthesis: 5g of tris (2-bromo-3-hydroxy-4-tert-butylpyridine) phosphite (L-2 a-Br) was dissolved in 7.5g of 1, 2-dichloroethane as a porogenic solvent under an argon atmosphere, and 0.05g of Ni (cod) was added thereto 2 Stirring at 20deg.C for 200 hr, adding 100mL of water to stop the reaction, filtering, and adding anhydrous CaCl 2 Drying, repeatedly washing the solid with water, performing Soxhlet extraction for 24 hours by using diethyl ether as a solvent, and then performing vacuum drying at 20 ℃ for 48 hours to obtain a tris (5, 5 '-di-tert-butyl-2, 2' -bipyridine) phosphite polymer (POL-2 a);
in the embodiment, the silica gel column is used for chromatographic purification, the adopted silica gel is sieved by a 100-200-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and absolute methanol according to the mass ratio of 20:1.
Example 7
The monophosphite ligand precursor adopts 4-hydroxy-3-tertiary butyl pyridine (shown as a compound 3 a) as R in the compound 3 2 is-tBu (tert-butyl, also known as-CC (CH) 3 ) 3 )，R 1 A compound which is-H;
a preparation method of a hydrophobic bisphosphite organic polymer is characterized in that: the method comprises the following steps:
(1) Halogenation reaction: adding 100mL of methylene dichloride into 1.0mol of 4-hydroxy-3-tert-butylpyridine (3 a) at the temperature of minus 20 ℃, slowly adding 100mL of bromine water with the concentration of 0.01mol/mL as a halogenating reagent into the mixture after dissolution, carrying out heat preservation and stirring reaction for 72h, carrying out vacuum concentration, adding acetonitrile for redissolving, and purifying by silica gel column chromatography to obtain 3-bromo-4-hydroxy-5-tert-butylpyridine (3 a-Br);
(2) Esterification reaction: dissolving 0.8mol of 3-bromo-4-hydroxy-5-tert-butylpyridine (3 a-Br) obtained in step (1) and sodium carbonate (acid binding agent) in N, N-dimethylformamide under argon atmosphere at 30 ℃, and slowly adding PCl into the mixture 3 Wherein PCl 3 The mol ratio of 3-bromo-4-hydroxy-5-tert-butylpyridine to acid binding agent is 1:4:10, the reaction is carried out for 72h under heat preservation and stirring, 100mL of water is added to stop the reaction, and the reaction is carried out by extracting with ethyl acetate, washing the organic layer with saturated saline solution and anhydrous CaCl 2 Drying, vacuum concentrating, purifying by silica gel column chromatography to obtain tri (3-bromo-5-tert-butylpyridine) phosphite, which is denoted as L-3a-Br;
(3) And (3) polymer synthesis: under an argon atmosphere, 5g of tris (3-bromo-5-t-butylpyridinium) phosphite (L-3 a-Br) was dissolved in a pore-forming solvent of 500-g N-methylpyrrolidone, to which 0.5g of Ni (COD) was added 2 Stirring at 80deg.C for 200 hr, adding 100mL water to stop the reaction, filtering, and adding anhydrous CaCl 2 Drying, repeatedly washing the solid with water, soxhlet extracting with diethyl ether for 36h, and vacuum drying at 80deg.C for 2h to obtain hydrophobic bisphosphite organic polymerAnd (3) the following substances: tris (5, 5 '-di-tert-butyl-4, 4' -bipyridine) phosphite, designated POL-3a:
in the embodiment, the silica gel column is used for chromatographic purification, the adopted silica gel is sieved by a 100-200-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and absolute methanol according to the mass ratio of 20:1.
Example 8
The 3-hydroxy-2-tert-butylpyridine (denoted as compound 4 a) is used as R in the compound 4 according to the invention as the monophosphite ligand precursor 2 is-tBu, R 1 A compound which is-H;
a preparation method of a hydrophobic bisphosphite organic polymer is characterized in that: the method comprises the following steps:
(1) Halogenation reaction: 1000mL of acetonitrile is added into 3128g (10 mol) of 3-hydroxy-2-tert-butylpyridine (4 a) at 25 ℃, after dissolution, 1780g (10 mol) of N-bromosuccinimide is slowly added into the mixture as a halogenating reagent, the mixture is stirred for reaction for 72 hours under heat preservation, vacuum concentration is carried out, acetonitrile is added for dissolution again, and 4-bromo-3-hydroxy-2-tert-butylpyridine (4 a-Br) is obtained after silica gel column chromatography purification;
(2) Esterification reaction: 5mol of 4-bromo-3-hydroxy-2-tert-butylpyridine (4 a-Br) obtained in step (1) and 10mol of potassium carbonate (acid-binding agent) were dissolved in 1, 2-dichloroethane under an argon atmosphere at 30℃and 1mol of PCl was slowly added thereto 3 Stirring at a constant temperature for 0.5h, adding 100mL of acetic acid to stop the reaction, extracting with ethyl acetate, washing the organic layer with saturated saline solution, and adding anhydrous CaCl 2 Drying, vacuum concentrating, and purifying by silica gel column chromatography to obtain sub-componentTris (4-bromo-2-tert-butylpyridine) phosphate, designated L-4a-Br;
(3) And (3) polymer synthesis: 5g of tris (4-bromo-2-t-butylpyridinium) phosphite was dissolved in 200-g N-methylpyrrolidone as a porogenic solvent, to which 0.5g of Ni (cod) was added 2 Stirring under argon atmosphere at 170deg.C for 0.1 hr, adding 100mL acetic acid to stop reaction, filtering, and anhydrous CaCl 2 Drying, repeatedly washing the solid with acetone, performing Soxhlet extraction with diethyl ether as a solvent for 36h, and then performing vacuum drying at 80 ℃ for 2h to obtain a hydrophobic bisphosphite organic polymer tris (5, 5 '-di-tert-butyl-3, 3' -bipyridine) phosphite, which is marked as POL-4a;
in the embodiment, the silica gel column chromatography is used for purification, the adopted silica gel is sieved by a 100-200-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and ethyl acetate according to the mass ratio of 20:1.
Example 9
The monophosphite ligand precursor uses 3-tert-butyl-2-naphthol (noted as compound 5 a) as R in compound 5 of the present invention 2 Is tBu, R 1 A compound which is H;
a method for preparing a hydrophobic bisphosphite organic polymer, comprising the steps of:
(1) Halogenation reaction: adding 100mL of acetonitrile into 1mol of 3-tert-butyl-2-naphthol (5 a) at 80 ℃, dissolving, slowly adding 1mol of iodine simple substance into the mixture as a halogenated reagent, carrying out heat preservation and stirring reaction for 24 hours, concentrating in vacuum, adding acetonitrile for redissolving, and purifying by silica gel column chromatography to obtain 1-bromo-3-tert-butyl-2-naphthol (5 a-Br);
(2) Esterification reaction: after 0.6mol of 1-bromo-3-tert-butyl-2-naphthol (5 a-Br) obtained in step (1) and 1.2mol of pyridine (acid-binding agent) were dissolved in DMF under an argon atmosphere at 100℃and 0.1mol of PCl was slowly added thereto 3 Stirring at constant temperature for 0.5h, adding 100mL sodium bicarbonate aqueous solution to stop the reaction, extracting with ethyl acetate, washing the organic layer with saturated saline solution, vacuum concentrating, and concentrating with anhydrous Na 2 SO 4 Drying and silica gel column chromatography purification are carried out to obtain tri (1-bromo-3-tert-butyl-2-naphthol) phosphite, which is marked as L-5a-Br:
(3) And (3) polymer synthesis: 5g of tris (1-bromo-3-tert-butyl-2-naphthol) phosphite (L-5 a-Br) was dissolved in 50g of xylene as a porogenic solvent, to which 5g of Ni (cod) was added 2 Stirring under argon atmosphere at 250deg.C for 12 hr, adding 100mL of water to stop the reaction, filtering, and using anhydrous Na 2 SO 4 Drying, repeatedly washing the solid with water, performing Soxhlet extraction with diethyl ether as a solvent for 72 hours, and then performing vacuum drying at 80 ℃ for 2 hours to obtain the hydrophobic bisphosphite organic polymer: tris (3, 3' -di-tert-butyl-binaphthyl) phosphite polymer, designated POL-5:
in the embodiment, the silica gel column chromatography is used for purification, the adopted silica gel is sieved by a 100-200-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and ethyl acetate according to the mass ratio of 20:1.
Example 10
The monophosphite ligand precursor uses 3-tert-butyl-2-pyrrole (noted as compound 6 a) as R in compound 6 of the present invention 2 is-tBu, R 1 is-H, X 2 A compound that is-NH;
a preparation method of a hydrophobic bisphosphite organic polymer is characterized in that: the method comprises the following steps:
(1) Halogenation reaction: adding 100mL of acetonitrile into 1mol of 3-tert-butyl-2-hydroxypyrrole (6 a) at 25 ℃, dissolving, slowly adding 3mol of N-bromosuccinimide into the mixture as a halogenating reagent, carrying out heat preservation and stirring reaction for 72h, concentrating in vacuum, adding acetonitrile for redissolving, and purifying by silica gel column chromatography to obtain 1-bromo-3-tert-butyl-2-hydroxypyrrole (6 a-Br);
(2) Esterification reaction: dissolving 1mol of 1-bromo-3-tert-butyl-2-pyrrole (6 a-Br) obtained in step (1) and potassium carbonate (acid binding agent) in ethyl acetate at 30 ℃ under argon atmosphere, and slowly adding PCl 3 Wherein PCl 3 The mol ratio of the 1-bromo-3-tert-butyl-2-pyrrole to the acid-binding agent is 1:3:9, the reaction is carried out for 72h under heat preservation and stirring, 100mL of water is added to stop the reaction, the organic layer is washed by saturated saline water after extraction by ethyl acetate, and anhydrous Na is used 2 SO 4 Drying, vacuum concentrating, and purifying by silica gel column chromatography to obtain tri (1-bromo-3-tert-butylpyrrole) phosphite, which is marked as L-6a-Br:
(3) And (3) polymer synthesis: 5g of tris (1-bromo-3-t-butylpyrrole) phosphite (L-6 a-Br) was dissolved in 200-g N-methylpyrrolidone as a porogenic solvent, to which 0.5g of Ni (cod) was added 2 Stirring under argon atmosphere at 60deg.C for 100 hr, adding 100mL water to stop reaction, filtering, and using anhydrous Na 2 SO 4 Drying, repeatedly washing the solid with water, performing Soxhlet extraction with diethyl ether as a solvent for 36h, and then performing vacuum drying at 80 ℃ for 2h to obtain a hydrophobic bisphosphite organic polymer tris (4, 4 '-di-tert-butyl-2, 2' -bipyrrole) phosphite polymer, which is marked as POL-6a:
in the embodiment, the silica gel column chromatography is used for purification, the adopted silica gel is sieved by a 100-200-mesh sieve, and the chromatographic agent is mixed liquid of n-hexane and ethyl acetate according to the mass ratio of 20:1.
Claims (7)
1. A preparation method of a hydrophobic bisphosphite organic polymer is characterized in that: the method comprises the following steps:
(1) Halogenation reaction: adding a solvent A into the monophosphite ligand precursor at the temperature of minus 20-80 ℃, adding a halogenated reagent into the monophosphite ligand precursor after dissolution, carrying out heat preservation and stirring reaction for 0.5-72h, carrying out vacuum concentration, adding the solvent A for redissolving, and purifying to obtain the halogenated monophosphite ligand precursor;
(2) Esterification reaction: mixing and dissolving halogenated monophosphite ligand precursor, acid binding agent and solvent B in inert gas atmosphere at-80-160 ℃, and adding PCl into the mixture 3 Or PBr 3 Stirring at constant temperature for 0.5-72 hr, adding water or acidic solution to stop the reaction, extracting with organic solvent, washing the organic layer with saturated saline solution, vacuum concentrating, and concentrating with anhydrous Na 2 SO 4 、CaCl 2 Or MgSO 4 Drying and purifying to obtain a monophosphite ligand;
(3) And (3) polymer synthesis: dissolving a monophosphite ligand in a pore-forming solvent under inert gas atmosphere, adding a coupling catalyst into the solution, stirring the solution at the temperature of minus 20 ℃ to 170 ℃ for reaction for 0.1 to 200 hours, adding water or an acidic solution for stopping the reaction, and filtering the solution, and then using anhydrous Na 2 SO 4 、CaCl 2 Or MgSO 4 Drying, washing the solid with water, absolute ethyl alcohol or absolute methyl alcohol, performing Soxhlet extraction for 12-72 hours, and then performing vacuum drying to obtain a hydrophobic bisphosphite organic polymer; the monophosphite ligand precursor comprises any one of compounds 1-6 shown in the following structural formula:
wherein R is 1 =H，Me，Et，Pr；R 2 ，R 3 =H，iPr，tBu；X 2 =N，O，S；
The molar ratio of the halogenating agent to the monophosphite ligand precursor is 0.1-10;
in step (2), PCl 3 The mol ratio of the halogenated monophosphite ligand precursor to the acid binding agent is 1 (2-6): 4-12;
in step (3), the monophosphite ligand: pore-forming solvent: the mass ratio of the coupling catalyst is 1: (1.5-100): (0.01-10).
2. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein:
the acid binding agent is triethylamine, pyridine, benzothiazole, naOH, KOH or potassium carbonate.
3. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein:
the solvent B is any one or more of methanol, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, N-hexane, petroleum ether, ethyl acetate, N-dimethylformamide, acetone, benzene or benzene homologs and 1, 2-dichloroethane.
4. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein: the coupling catalyst is one of tri (triphenylphosphine) nickel, bis- (1, 5-cyclooctadiene) nickel, bis (triphenylphosphine) - (1, 5-cyclooctadiene) nickel, bis (1, 2-bis (4-trifluoromethylstyrene) ethylene) nickel or bis (triphenylphosphine) ethylene nickel.
5. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein: the pore-forming solvent is at least one of methanol, ethanol, acetonitrile, tetrahydrofuran, ethyl acetate, N-dimethylformamide, acetone, N-methylpyrrolidone, benzene or benzene homologs, biphenyl, bipyridine and 1, 2-dichloroethane.
6. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein: the halogenated reagent in the step (1) is F 2 、Cl 2 、Br 2 、I 2 HCl, HBr, N-iodosuccinimide, N-bromosuccinimide, N-chlorosuccinimide, methyl iodide or methyl bromide; the solvent A is acetonitrile or tetrahydrofuran.
7. The process for preparing a hydrophobic bisphosphite organic polymer according to claim 1, wherein: the purification adopts a silica gel column chromatography purification or solvent recrystallization method; the silica gel in the silica gel column chromatography purification is 100-400 meshes of silica gel; the chromatographic agent used in the silica gel column chromatography purification or the recrystallization solvent used in the solvent recrystallization method is one or more of absolute methanol, absolute ethanol, ethyl acetate, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, normal hexane, petroleum ether and N, N-dimethylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446279.0A CN114685762B (en) | 2022-04-26 | 2022-04-26 | Preparation method of hydrophobic bisphosphite organic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446279.0A CN114685762B (en) | 2022-04-26 | 2022-04-26 | Preparation method of hydrophobic bisphosphite organic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114685762A CN114685762A (en) | 2022-07-01 |
| CN114685762B true CN114685762B (en) | 2023-09-05 |
Family
ID=82145892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210446279.0A Active CN114685762B (en) | 2022-04-26 | 2022-04-26 | Preparation method of hydrophobic bisphosphite organic polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685762B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA759472A (en) * | 1967-05-23 | F. Baranauckas Charles | Tetrachloro bisphenol bisphosphites | |
| EP0312915A2 (en) * | 1987-10-19 | 1989-04-26 | Ethyl Corporation | Process for making cyclic aryl chlorophosphites |
| JP2001170490A (en) * | 1999-12-17 | 2001-06-26 | Tosoh Corp | Catalyst for cross coupling reaction and method for manufacturing aromatic allyl derivative usinf the same |
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| WO2011120686A1 (en) * | 2010-03-31 | 2011-10-06 | Styron Europe Gmbh | Thermally oxidatively stable carbonate phosphite copolymer |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
| CN103288995A (en) * | 2013-06-09 | 2013-09-11 | 浙江大学 | Preparation method of porous polytriphenylphosphine material |
| CN103965386A (en) * | 2014-05-05 | 2014-08-06 | 浙江大学 | Preparation method for porous poly diphosphine ligand material |
| CN104017022A (en) * | 2014-05-09 | 2014-09-03 | 广州合成材料研究院有限公司 | Method for preparing phosphite antioxidant |
| CN104098601A (en) * | 2014-06-27 | 2014-10-15 | 同济大学 | Allyl phosphite ester compound and synthesizing method thereof |
| CN104292255A (en) * | 2014-01-06 | 2015-01-21 | 郑州大学 | Preparation method of S-aryl phosphorothioate |
| CN105859795A (en) * | 2016-04-08 | 2016-08-17 | 苏州大学 | Phosphite/N-heterocyclic carbene-containing mixed nickel (II) complex, and preparation method and application thereof |
| CN107915757A (en) * | 2017-11-21 | 2018-04-17 | 郑州大学 | Using trans cvclohexvl glycol as bidentate phosphite ester ligand of connection structure and preparation method thereof |
| CN108129515A (en) * | 2017-12-05 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of bis-phosphite |
| CN111848683A (en) * | 2020-07-16 | 2020-10-30 | 南方科技大学 | Biphenyl tridentate phosphite ligand and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331584A (en) * | 2003-05-08 | 2004-11-25 | Sumitomo Chem Co Ltd | Method for producing phosphorous ester |
| US11306112B2 (en) * | 2020-02-10 | 2022-04-19 | Guangdong Oxo Chem Ltd. | Biphenyl tetradentate phosphite compound: preparation method and application thereof |
-
2022
- 2022-04-26 CN CN202210446279.0A patent/CN114685762B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA759472A (en) * | 1967-05-23 | F. Baranauckas Charles | Tetrachloro bisphenol bisphosphites | |
| EP0312915A2 (en) * | 1987-10-19 | 1989-04-26 | Ethyl Corporation | Process for making cyclic aryl chlorophosphites |
| JP2001170490A (en) * | 1999-12-17 | 2001-06-26 | Tosoh Corp | Catalyst for cross coupling reaction and method for manufacturing aromatic allyl derivative usinf the same |
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| WO2011120686A1 (en) * | 2010-03-31 | 2011-10-06 | Styron Europe Gmbh | Thermally oxidatively stable carbonate phosphite copolymer |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
| CN103288995A (en) * | 2013-06-09 | 2013-09-11 | 浙江大学 | Preparation method of porous polytriphenylphosphine material |
| CN104292255A (en) * | 2014-01-06 | 2015-01-21 | 郑州大学 | Preparation method of S-aryl phosphorothioate |
| CN103965386A (en) * | 2014-05-05 | 2014-08-06 | 浙江大学 | Preparation method for porous poly diphosphine ligand material |
| CN104017022A (en) * | 2014-05-09 | 2014-09-03 | 广州合成材料研究院有限公司 | Method for preparing phosphite antioxidant |
| CN104098601A (en) * | 2014-06-27 | 2014-10-15 | 同济大学 | Allyl phosphite ester compound and synthesizing method thereof |
| CN105859795A (en) * | 2016-04-08 | 2016-08-17 | 苏州大学 | Phosphite/N-heterocyclic carbene-containing mixed nickel (II) complex, and preparation method and application thereof |
| CN107915757A (en) * | 2017-11-21 | 2018-04-17 | 郑州大学 | Using trans cvclohexvl glycol as bidentate phosphite ester ligand of connection structure and preparation method thereof |
| CN108129515A (en) * | 2017-12-05 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of bis-phosphite |
| CN111848683A (en) * | 2020-07-16 | 2020-10-30 | 南方科技大学 | Biphenyl tridentate phosphite ligand and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钯催化剂催化交叉偶联反应形成Ｐ－Ｃ键和 复杂含磷化合物的研究进展;任铁钢 等;化学研究;第25卷(第6期);第641-647页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114685762A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6227147B2 (en) | Polymer containing carboxyl group, production method and use thereof, supported metal catalyst and method for producing penem antibiotic intermediate | |
| US20220106340A1 (en) | Acylphosphine oxide compounds and preparation methods thereof | |
| CA2913520A1 (en) | Synthesis of alpha, beta-unsaturated carboxylic acid (meth)acrylates from olefins and co2 | |
| CN109453814B (en) | Multi-level pore polymer supported rhodium catalyst containing sulfonic group and phosphine ligand, preparation and application thereof | |
| CN104844411A (en) | Method for synthesizing hexafluoro-1,3-butadiene | |
| CN114685762B (en) | Preparation method of hydrophobic bisphosphite organic polymer | |
| JP2007302859A (en) | NEW TRANSITION METAL COMPLEX CARRIED BY POLYMER USING p-PHOSPHINE GROUP-CONTAINING STYRENE-STYRENE-BASED COPOLYMER AS LIGAND, AND CATALYST COMPRISING THE COMPLEX | |
| US11021499B2 (en) | Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, ammonium salt thereof, and method for producing same | |
| CN112756012B (en) | Hydrophilic organic porous polymer supported palladium catalyst, and preparation method and application thereof | |
| Liu et al. | Polymer-supported tertiaryphosphine (JJ–TPP) as a green and recyclable organocatalyst for α-addition of carbon nucleophiles to α, β-unsaturated compounds | |
| CN113956289A (en) | Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction | |
| CN105289736A (en) | Preparation method of acetylacetone dioxaphosphepin | |
| Ji et al. | Titanium phosphonate-supported palladium catalyst for the hydrogenation of acetophenone with one-phase catalysis and two-phase separation | |
| KR100875805B1 (en) | Method for preparing 2,3,6,7,10,11-hexahydroxytriphenylene | |
| CN112759616B (en) | Tri-discoene carbene palladium compound and application thereof | |
| CN114057791B (en) | Hydrolysis-resistant phosphite ligand, preparation method and application of phosphite ligand in preparation of linear aldehyde by catalyzing olefin hydroformylation reaction | |
| CN110655533B (en) | Preparation method of 4- (diethoxy-phosphoryl) -2-methyl-butyl-2-olefine acid ester | |
| CN110683949B (en) | Method for preparing 9, 10-phenanthrene dicarboxylic ester compound | |
| KR102217415B1 (en) | Bis(6-methyl-3-sulphophenyl)phenylphosphine, ammonium salt thereof, and method for producing same | |
| CN116217320A (en) | Heterogeneous catalysis alkyne and azide axial chiral Click synthesis method | |
| CN115838364A (en) | Synthetic method of 3, 3-bithiophene | |
| CN117777198A (en) | Triarylphosphine compound based on phosphafluorene structure and preparation method thereof | |
| Huang et al. | Development of 3-methoxy-4-benzyloxybenzyl alcohol (MBBA) resin as polymer-supported synthesis support: Preparation and benzyl ether cleavage by DDQ oxidation | |
| CN115246762A (en) | Preparation method of 2,4,5-trifluorophenylacetic acid | |
| CN114315895A (en) | Ligand, preparation method and application thereof, and method for preparing linear dialdehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |